CN1243822A - Process for preparing monomer of cathionic polymer - Google Patents
Process for preparing monomer of cathionic polymer Download PDFInfo
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- CN1243822A CN1243822A CN 99114784 CN99114784A CN1243822A CN 1243822 A CN1243822 A CN 1243822A CN 99114784 CN99114784 CN 99114784 CN 99114784 A CN99114784 A CN 99114784A CN 1243822 A CN1243822 A CN 1243822A
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- propenyl chloride
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- dimethylamine
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Abstract
A process for preparing cationic polymer monomer, ammonium dimethyldienepropyl chloride, uses chloropropylene, dimethylamine and sodium hydroxide as raw materials in equal mole ratio, and features that one-step synthesis process is used where alkali and chloropropylene are alternatively added at low pressure and high temp in enclose condition. Its advantages include no need of separating intermediate, less steps, high reaction speed, high output, low cost and no waste discharge. Said monomer can be used to synthesize water-soluble polymer containing organic cations, such as oil-displacing agent, treating agent of drilling liquid and disinfectant.
Description
The present invention relates to the synthetic of a kind of cationic monomer diallyldimethylammonChloride Chloride, it is to adopt " single stage method " polystep reaction of synthesization of dimethyl diallyl ammonium chloride is realized in a reactor, belongs to the preparation method of monomer of cathionic polymer.
Monomer of cathionic polymer dimethyl diallyl ammonium chloride (Dimethyl DiallylAmmonium Chloride) is called for short DMDAAC.Molecular weight 161.6, CAS registration number [7398-69-8], pure product are colorless solid, and are soluble in water, very easily the moisture absorption.Its structural formula is: (CH
3)
2N
+(CH
2CH=CH
2)
2Cl
-Its building-up reactions has following three steps usually:
(1) tertiary amine reaction
(2) neutralization reaction
(3) quaterisation
Main side reaction is dimethylamine and intermediate tertiary amine and hydrogenchloride formation hydrochloride, and the macromolecule alkali for hydrolysis of the propenyl chloride of N-process:
DMDAAC is mainly used in to synthesize and contains organic cationic water-soluble polymers, can improve water-soluble, the rheology of solution of polymkeric substance, increases adsorptive power and sterilizing ability etc.DMDAAC is used for synthesizing new polymer oil-displacing agent and additive for drilling fluid, water conditioner and sterilant, also is widely used on day chemical industry and the paper industry, and the market consumption is increasing.
Realized the suitability for industrialized production of DMDAAC at present both at home and abroad, because its conventional production process is comparatively complicated, side reaction is many, and reaction and operation steps are many, and it is low that transformation efficiency changes, and causes to cost an arm and a leg.At present from domestic and international related data, the method for preparing DMDAAC adopts atmospheric low-temperature technology more, raw material and intermediate need purifying, as Hunter, Wood E.Sieder, Theodore P. (US 4151202A, 1979) employing filtration after washing is washed technology and is come the purifying propenyl chloride, then at atmospheric low-temperature (＜47 ℃) and the synthetic DMDAAC of dimethylamine reaction; The perhaps reactant inequality that feeds intake, as Ballschuh, Detlef; Jaeger, Werner; Et al. (GB 1573239A, 1980) adopt the 100mol dimethylamine to add in the 25mol propenyl chloride down at 15 ℃, add the 185mol propenyl chloride then rapidly, and the maintenance temperature is slowly and equably to add 100mol 50%NaOH solution under 15 ℃, charge into behind the nitrogen reheat to 100 and ℃ kept 2 hours, propenyl chloride excessive 5% in this technology; People such as the gorgeous plum of domestic power, Hu Xuguang adopt improved DMDAAC synthetic with analytical procedure (oilfield chemistry, 1997, Vol 14, No 2:159-161), normal pressure synthesis, underpressure distillation and filtration are purified, product yield can reach about 85%; Xu Yanli (petrochemical complex, 1998, Vol 27, No.7:517-520) adopt alternate feeding, substep heating, and propenyl chloride is excessive 5.0～7.5%, and 45 ℃ of reactions 6～7 hours, the yield that provides DMDAAC at last is the highest can to reach 92%.Because main raw material dimethylamine (CH
3)
2NH and propenyl chloride CH
2=CHCH
2The boiling point of Cl is lower than 45 ℃, makes that the synthesis under normal pressure temperature is low, long reaction time, and propenyl chloride and dimethylamine are difficult to total condensation under the room temperature, and highly volatile loss, so reactant feed ratio inequality always cause that yield is low, environmental pollution is big, production cost is high.These major defects cause the DMDAAC turnout too little, and market is in short supply, have greatly limited its industrial production and have used.
The objective of the invention is to overcome existing atmospheric low-temperature preparation technology's defective, propose a kind of novel preparation method with high speed of response, high yield, high quality and low cost, oligosaprobic cationic monomer diallyldimethylammonChloride Chloride.
Its major technique feature of preparation method provided by the invention is: adopt airtight low pressure, high temperature, reaction with same mole thing proportioning, alternately add the synthetic DMDAAC of " single stage method " novel process of alkali and propenyl chloride.With technical grade propenyl chloride, dimethylamine and sodium hydroxide is raw material, according to reaction with same mole thing proportioning, operates in closed reactor.Preparation method of the present invention is: earlier in reactor, add a certain amount of 40% dimethylamine solution, closed reactor also stirs, slowly add equimolar propenyl chloride again, under low pressure (less than 0.2MPa) condition, control reaction temperature alternately adds alkali (NaOH solution) and propenyl chloride again and makes the acid or alkali environment of reaction system approaching neutral at 65～85 ℃, and synthesising reacting time needs 2 hours approximately.This preparation method be because temperature of reaction can be brought up to 65～85 ℃ and be not subjected to the limitation of 45 ℃ of the boiling points of propenyl chloride, thereby accelerated speed of response.Make reaction system PH for neutral owing to alternately add alkali and propenyl chloride, solved the contradiction between the nucleophilic reaction activity of avoiding the propenyl chloride hydrolysis and keeping amine well.After tertiary amineization and neutralization reaction, will not separate by intermediate allyl dimethyl base amine, and directly carry out next step quaterisation, realize that single stage method synthesizes with propenyl chloride.Adopt two constant voltage test tanks that have muffler during production, respectively propenyl chloride and alkaline solution are with the pressure alternate feeding.In concentration process, adopt shell and tube vacuum diaphragm vaporizer, realize that low temperature concentrates fast, the easy crystallization of by product sodium-chlor is separated out, help removing by filter.
The preparation method of product of the present invention compared with prior art has following advantage:
(1) do not separate intermediate product, and direct and next step raw material reaction, thereby the three-step reaction operation can be reduced to a step, improve quality product, reduced production cost.
(2) to have operation steps less for this technology, because of temperature of reaction is increased to 65～85 ℃, and accelerated speed of response, shortened the time of whole process of production.
(3) can realize reaction with same mole thing feed ratio, reactant molar ratio according to reaction equation is: propenyl chloride: dimethylamine: sodium hydroxide=2.0: 1.0: 1.0, improved transformation efficiency, and yield is up to 95%, and cost is low, does not produce three waste discharge on technology.
Further specify the production implementing method of this invention below in conjunction with technical scheme provided by the invention:
Ward off in the glass reactor at 0.25m3, pump into 40% dimethylamine solution 620mol, closed reactor also stirs, and slowly adds propenyl chloride 620mol by the constant voltage test tank, adds in about 40～60 minutes.Controlled temperature is lower than 65 ℃, and pressure is lower than 0.2MPa (gauge pressure).620mol NaOH is dissolved in the 60Kg water, alternately adds for 5～10 times by constant voltage test tank average mark, added in about 1～2 hour with other 620mol propenyl chloride.Control reaction temperature keeps the still internal pressure to be lower than 0.2MPa at 65～85 ℃.Detect to PH every sampling in 30 minutes and to be neutral (6.5-8.5), and refractive index is constant, finish reaction.This process needs 2 hours approximately.With reaction mixture whizzer solids removed by filtration thing sodium-chlor.Mother liquor is about 50% DMDAAC, carry out vacuum concentration (55～65 ℃ of temperature with the vacuum diaphragm vaporizer, pressure less than-0.08MPa), the concentration (refractive index method) that is concentrated into DMDAAC after about 40 minutes is when reaching 75～85 ℃, after leaching crystallization sodium-chlor, mother liquor continue is concentrated, obtain content at last and reach lenticular cationic monomer DMDAAC more than 98%.
Claims (4)
1. the preparation method of a monomer of cathionic polymer dimethyl diallyl ammonium chloride, it is characterized in that: with the technical grade propenyl chloride that waits the mole proportioning, dimethylamine and sodium hydroxide are raw material, adopt airtight low pressure, high temperature, " single stage method " synthesization of dimethyl diallyl ammonium chloride that alternately adds alkali and propenyl chloride, in reactor, add a certain amount of dimethylamine solution earlier, airtight and stir, slowly add equimolar propenyl chloride again, under low pressure and comparatively high temps, alternately add acid-basicity that alkaline solution and propenyl chloride make reaction system again near neutral reaction 1～2 hour, at last mother liquor is filtered, concentrate and to get content and reach crystal cationic monomer more than 98%.
2. preparation method according to claim 1 is characterized in that: temperature of reaction is controlled at 65～85 ℃, and seal-off pressure is less than 0.2MPa, and pH value is near neutral (6.5～8.5).
3. preparation method according to claim 1, it is characterized in that: raw materials used proportioning (mol ratio) is, propenyl chloride: dimethylamine: sodium hydroxide=2.0: 1.0: 1.0, respectively propenyl chloride and alkaline solution are with the pressure alternate feeding by two constant voltage test tanks that have muffler.
4. preparation method according to claim 1 is characterized in that: with shell and tube vacuum diaphragm vaporizer concentration of reaction solution, realize that low temperature concentrates fast, and 55～65 ℃ of service temperatures, pressure is less than-0.08MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99114784A CN1089087C (en) | 1999-04-09 | 1999-04-09 | Process for preparing monomer of cathionic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99114784A CN1089087C (en) | 1999-04-09 | 1999-04-09 | Process for preparing monomer of cathionic polymer |
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| Publication Number | Publication Date |
|---|---|
| CN1243822A true CN1243822A (en) | 2000-02-09 |
| CN1089087C CN1089087C (en) | 2002-08-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99114784A Expired - Fee Related CN1089087C (en) | 1999-04-09 | 1999-04-09 | Process for preparing monomer of cathionic polymer |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006069504A1 (en) * | 2004-12-31 | 2006-07-06 | Nanjing University Of Science & Technology | A purification method for the cationic monomer of dimethyldiallylammonium chloride with high purity |
| CN101906050A (en) * | 2010-06-07 | 2010-12-08 | 浙江华晟化学制品有限公司 | Preparation method of dimethyldiallylammonium chloride monomer |
| CN109438250A (en) * | 2018-12-20 | 2019-03-08 | 山东天成化工有限公司 | A kind of preparation method of high purity dimethyl diallyl ammonium chloride monomer high yield |
| CN114212869A (en) * | 2021-12-09 | 2022-03-22 | 苏州业华环境科技有限公司 | Preparation method of polycation polymer, compound oil removal agent and oil removal process |
-
1999
- 1999-04-09 CN CN99114784A patent/CN1089087C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006069504A1 (en) * | 2004-12-31 | 2006-07-06 | Nanjing University Of Science & Technology | A purification method for the cationic monomer of dimethyldiallylammonium chloride with high purity |
| CN1323064C (en) * | 2004-12-31 | 2007-06-27 | 南京理工大学 | High purity cationic monomer diallyldimethylammonium Chloride refining method |
| CN101906050A (en) * | 2010-06-07 | 2010-12-08 | 浙江华晟化学制品有限公司 | Preparation method of dimethyldiallylammonium chloride monomer |
| CN109438250A (en) * | 2018-12-20 | 2019-03-08 | 山东天成化工有限公司 | A kind of preparation method of high purity dimethyl diallyl ammonium chloride monomer high yield |
| WO2020140187A1 (en) * | 2018-12-20 | 2020-07-09 | 山东天成化工有限公司 | Method for preparing high purity dimethyl diallyl ammonium chloride monomer in high yield |
| CN114212869A (en) * | 2021-12-09 | 2022-03-22 | 苏州业华环境科技有限公司 | Preparation method of polycation polymer, compound oil removal agent and oil removal process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1089087C (en) | 2002-08-14 |
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